Sulfuric acid ester derivatives of 1-anilino - 4 - hydroxy - anthraquinone and mixtures



United States Patent 3,421,828 SULFURIC ACID ESTER DERIVATIVES 0F 1- ANILINO 4 HYDROXY ANTHRAQUINONE AND MIXTURES Hans Peter Kolliker, Munchenstein, Basel-Land, and Peter Hindermann, Batterie, Bottmingen, Switzerland, assignors to J. R. Geigy A.G., Basel, Switzerland No Drawing. Filed July 16, 1964, Ser. No. 383,254 Claims priority, application Switzerland, July 19, 1963, 9,050/63, 9,051/63; June 3, 1964, 7,239/64 US. Cl. 825 17 Claims Int. Cl. C09b 1/52 ABSTRACT OF THE DISCLOSURE The present invention provides new substituted a-phenylamino-anthraquinone dyestuffs. In a first aspect there are provided dyestuffs falling under one of the formulas:

in which formulas the respective symbols have the following meanings:

one of X and X represents hydroxy and the other represents hydroxy, nitro, amino, N-lower alkyl-a'mino, N,N-di-lower alkyl-amino, 'N-lower alkoxy-N-lower a1- kyl-amino or hydroxy-lower alkylamino,

each of Y and Y represents hydrogen, chlorine or bromine,

R represents lower alkyl, alkenyl of from 2 to 4 carbon atoms, chloro-lower alkyl, chloro-lower alkenyl, cycloalkyl of from 5 to 7 carbon atoms, phenyl, chlorophenyl, bromophenyl, fluorophenyl, lower alkyl-phenyl,

lower alkoxy-phenyl, (chloro-lower alkyl)-phenyl, (lower alkyl-sulfonyl)-phenyl, (lower alkyl-carbonyl)- phenyl, (lower alkanoyl-amino)-phenyl, (N-lower alkyl-sulfonyl-N-lower alkyl)-phenyl, or pyridyl-3-oxy,

3,421,828 Patented Jan. 14, 1969 "ice Z represents from one to two of the following: hydrogen,

lower alkyl, lower alkoxy, chlorine, bromine, lower alkyl-sulfonyl, and lower alkyl-sulfonyl-amino, and

n has the above-given meaning;

preferably the benzene ring A is not further substituted or, if substituted, it contains chlorine, or methyl or methoxy.

In a pariicular aspect a dyestutf composition is provided consisting essentially of a dyestufl? of the formula NH O O mixed with a dyestuff of the formula in a weight ratio of about 1:1.

According to a second aspect of the invention dyestuffs are provided falling under one of the formulas NH2 (II) (FE Y0 30 0-32 H O NH A 2 I sol-041 X4 6 Z2 (IIIA) and H: O OH I I I (sot-04v) HO 0 NH A i Z2 (IIIB*) in which formulas the respective symbols have the following meanings:

n, X and X have the same meanings as in Formulas III, IIIA and 1118, respectively;

R represents alkyl of from 4 to carbon atoms, chlorolower alkyl, cycloalkyl of from 5 to 7 carbon atoms, phenyl, chlorophenyl, bromophenyl, fluorophenyl, lower alkylphenyl, lower alkoxyphenyl, chloro-lower alkyl-phenyl, (lower alkyl-sulfonyl)-phenyl, (lower a1- kyl-carbonyl)-phenyl, (lower alkanoyl-amino)-phenyl, (lower alkylsulfonyl)phenyl, (N-lower alkyl-sulfonyl- N-lower alkyl-amino)-phenyl, benzyl, chloro-benzyl, brorno-benzyl, lower alkyl-benzyl, or pyridyl-(3)-, and

Z represents from one to two of the following substituents: hydrogen, lower alkyl, lower alkoxy, chlorine and bromine.

In a further aspect a dyestuff composition is provided consisting essentially of a dyestufi of the formula OH H l we H l rn-om mixed with a dyestuff of the formula 111B; (1) OH in a weight ratio of about 1:1.

The present invention concerns new substituted u-phenyl-amino-anthraquinone dyestufiis, processes for the production thereof, processes for the dyeing of polymeric ester fibers, in particular of fibers obtained from polymeric esters of aromatic polycarboxylic acids with polyvalent alcohols using the new dyestuffs and, as industrial product, the fibers dyed by the aid of these dyestuifs.

It has been found that, according to a first aspect of the invention, valuable substituted a-phenylamino-anthraquinone dyestuffs are obtained by reacting an anthraquinone compound of the formula wherein of X and X one X is hydrogen or the hydroxyl group, the other X is hydrogen, the hydroxyl group and-if the first X is the hydroxyl group-the other X also represents the nitro group, the unsubstituted amino group or one which is substituted by a lower alkyl, lower alkoxy-lower alkyl or hydroXy-lower alkyl group,

X represents the hydroXyl group if X and X independently of each other represent hydrogen or the hydroxyl group and it represents the nitro group if one of X and X is the nitro group, the unsubstituted amino group or one which is substituted by lower alkyl, lower alkoxy or hydroxy-lower alkyl, and

Y and Y preferably represent hydrogen or, provided that each of X and X are hydrogen, each Y can also be halogen, e.g. chlorine or bromine,

with an amine of the formula HzN- wherein R represents an unsubstituted or substituted alkyl, al-

kenyl, cycloalkyl or aryl group, and n represents 1 or 2, preferably however 1, and

the benzene ring A is unsubstituted or further substituted by substituents which do not dissociate acid in water, in particular by halogen, lower alkyl or lower alkoxy groups, whereby depending on a corresponding substitution of the starting materials, there are formed preferred dyestuffs falling under one of the formulas n on Y t sol-non n 0 NI-I- A Z1 (III) X3 0 on I Y (OSOz-Rh X4 Z1 (IIIA) and osowrwn (I) l n 0 NH A in which formulas the respective symbols have the following meanings:

one of X and X represents hydroxy and the other rep resents hydroxy, nitro, amino, N-lower alkyl-amino, N,N-di-1ower alkyl-amino, N-lower alkoxy-N-lower alkyl-amino or hydroxy-lower alkyLaminO,

each of Y and Y represents hydrogen, chlorine or bromine,

R represents lower alkyl, alkenyl of from 2 to 4 carbon atoms, chloro-lower alkyl, chloro-lower alkenyl, cycloalkyl of from 5 to 7 carbon atoms, phenyl, chlorophenyl, bromophenyl, fluorophenyl, lower alkyl-phenyl, lower alkoxyphenyl, (chloro-lower alkyl)-phenyl, (lower alkyl-sulfonyD-phenyl, (lower alkyl-carbonyl)-phenyl, (lower alkanoyl-amino) -pheny1, (N-lower alkyl-sulfonyl-N-lower allcyD-phenyl, or pyridyl-S-oxy,

Z represents from one to two of the following: hydrogen, lower alkyl, lower alkoxy, chlorine, bromine, lower alkyl-sulfonyl, and lower alkyl-sulfonyl-arnino, and

n has the above-given meaning;

preferably the benzene ring A is not further substituted or, if substituted, it contains chlorine, or methyl or methoxy.

The greater part of the starting materials of Formula I usable according to the invention are known; examples thereof are: 1,4-dihydroxy-, 1,4,5-trihydroxy-, 1,4,5,8- tetrahydroxy-, 1,4-dihydroxy-6-chloro-, 1,4-dihydroxy-6,7-

dichloro-, 1,5-dinitro-4,8-dihydroxyor 1,8-dinitro-4,5-dihydroxyanthraquinone. In the two latter mentioned compounds, a nitro group can also be replaced by an amino group which may be substituted by a low alkyl, alkoxyalkyl or hydroxyalkyl group.

Lower when used in this specification and the appended claims in connection with alkyl, alkanoyl or alkoxy means radicals having from 1 to 4 carbon atoms and when used with alkenyl, it means a radical having from 2 to 4 carbon atoms.

Some of the amines of Formula II to be reacted with these compounds of Formula I are known or they can be produced in the known manner, for example by reacting one mol of a nitrophenol of the formula with n mol of a sulphonic acid chloride or bromide of the formula Ha1O SR wherein Hal represents chlorine or bromine and R has the meaning given in Formula II, and subsequently reducing the nitro group to the amino group. When R represents a halogenomethyl group, the reduction should be carried out under mild conditions.

The reaction of the starting materials of Formula I containing nitro groups with the amines of Formula II is performed, for example, with an excess of amine in the melt at about 100 to 250 C., advantageously however, in an organic solvent which boils at about 110 to 220 C. Suitable organic solvents are, e.g. aromatic hydrocarbons which may be halogenated or nitrated such as xylenes, or monochlorobenzene or dichlorobenzenes, or nitrobenzene, also alcohols such as as alkanols having at least 4 carbon atoms, e.g. butanol or amyl alcohol, or alkylene glycols and their' monoalkyl ethers. The preferred organic solvent is nitrobenzene.

Starting materials of Formula I which do not contain nitro groups are reacted with the amines of Formula II, preferably in the presence of boric acid or its alkali metal salts. In this reaction the starting materials of Formula I can also be used in the form of their leuco compounds or mixed with their leuco compounds.

If amines of Formula II are used in which both o-positions are further substituted, the use of a 1,3-alkane diol with boric acid, which diol forms with the boric acid a cyclic ester, or the use of a 1,3-alkane diol boric acid ester is recommended.

If the nitro group smybolised by X or X in the dyestuifs of Formula III is to be replaced by the amino group or by a low alkylamino, alkoxyalkylamino, or hydro-xyalkylamino group, this is done preferably by reducing the nitro group to the amino group and, if desired, substituting the latter by a low alkyl, ralkoxyalkyl or hydroxyalkyl group by means of a usual alkylating agent.

A modification of the process for the production of new substituted a-phenylaminoanthraquinone dyestuffs consists in reacting an anthraquinone compound of Formula IV X1 OH I II M I I (Own X2 0 NH A wherein Hal represents chlorine or bromine and R has the meaning given in Formula II,

(OHM

whereby the reaction conditions described in the first process pertain here too.

The compound of Formula IV is condensed with the sulphonic acid chloride or bromide of Formula V in the usual way, e.g. in an organic solvent which is inert to both reaction partners, optionally in the presence of an acid binding agent, preferably in aqueous-pyridine or aqueousalkaline solution or suspension.

The new substituted a-phenylamino-anthraquinones of Formula III generally crystallise out of the reaction mixture. They are isolated by filtration, dilution of the mixture with water or with a low alcohol or by removal of the organic solvent by distillation or steam distillation and they can be purified by recrystallisation.

In a pure state, the new dyestuffs are shimmering, crystalline, deeply coloured compounds. They dissolve in hot organic solvents with a pure violet to blue colour. From an aqueous dispersion they dye polymeric ester fibres, e.g. cellulose esters such as cellulose triacetate, preferably however fibres obtained from polymeric esters of aromatic polycarboxylic acids with polyvalent alcohols, e.g. polyethyleneglycol terephthalate fibres, in violet to blue shades.

Fibers obtained from polymeric esters of aromatic polycarboxylic acids with polyvalent alcohols are dyed with aqueous dispersions of the dyestuffs according to the invention preferably at temperatures of over 100 C. under pressure. Very good dyeings are also obtained by impregnating these fibres with concentrated, aqueous dispersions of the dyestuffs according to the invention, drying the squeezed out fabric and then fixing the dyeing at temperatures of 180 to 250 C. The dyeing can also be performed, however, at the boiling point of the water in the presence of carriers such as phenylphenol, polychlorobenzene compounds or similar auxiliaries.

In many cases, the drawing power and also the dispersibility of the dyestuffs in the dye liquor can be still further improved by mixing two or more dyestuffs of which at least one corresponds to Formula III. The violet to blue dyeings attained on the fibres mentioned with the dyestufiFs according to the invention have considerably better fastness to sublimation and, in particular, to light than dyeings obtained with known dyestuffs of similar constitution. They also have very good wet fastness properties.

The following examples illustrate the invention. Where not otherwise expressly stated, parts are given as parts by weight. The temperatures are in degrees centigrade. The relationship of parts by weight to parts by volume is as that of grammes to cubic centimetres.

EXAMPLE 1 16 parts of boric acid are added to a mixture of 18 parts of quinizarin, 6 parts of leucoquinizarin and 37.4 parts of methane sulphonic acid-3-aminophenyl ester and the whole is stirred for 1 hour in 50 parts of ethyl alcohol at 85. At the end of this time, the reaction mixture has become dark brown-violet coloured. After the addition of parts ethyl alcohol and of 0.5 part of sodium perborate, it is slowly allowed to cool to room temperature while stirring.

The reaction product which separates out in crystalline form of the formula OSO2CH is filtered off, washed with boiling methyl alcohol, hot water which has been made weakly alkaline and, finally, with hot water until the washing liquor is neutral, and dried.

The dyestufl can also be recrystallised from ethylene glycol monoethyl ether, chlorobenzene or pyridine. It forms beautiful dark crystals having a green-golden shimrner and melts at 209-210". It dissolves in organic solvents with a clear reddish violet and in concentrated sulphuric acid with a dark blue colour.

From an aqueous dispersion, it dyes polyethylene glycolterephthalate fibres in clear violet shades which are very fast to sublimation, light and wet.

The same dyestuff is also obtained if, instead of the 37.4 parts of methane sulphonic acid 3 aminophenyl ester, 21.8 parts of 3-aminophenol are used and the reaction is otherwise performed as described. The product which is isolated by filtration, is subsequently slurried in a mixture of 200 parts 'of water and pyridine (1:1) whereupon 17.2 parts of methane sulphonic acid chloride are added dropwise at 5-10 within 1 hour; the slurry is then heated for 2 hours at 40-5 0.

The reaction product which is practically completely separated out by dilution with 200 parts of water is obtained by filtration. It corresponds in every respect to the dyestutf obtained by the reaction first mentioned above.

EXAMPLE 2 33 parts of 1,5 dinitro 4,8 dihydroxyanthraquinone are slurried in 150 parts of nitrobenzene and, after the addition of 41.14 parts of methane sulphonic acid 4- amino phenyl ester, this suspension is heated to 180 within half an hour; the greater part of the reaction products are thus dissolved. The reaction mixture is kept for 3 hours at this temperature while stirring well, and the water formed during the reaction is continuously distilled off from the solution which gradually turns a clear blue colour.

On completion of the reaction, the solution is slowly cooled to room temperature while stirring constantly, whereupon the reaction product of the formula separates out in fine crystalline form. It is filtered 01f,

From an aqueous dispersion it dyes polyethylene glycolterephthalate fibres in particular in clear blue shades which have very good sublimation, light and Wet fastness properties.

If instead of the 41.14 parts of methane sulphonic acid- 4-aminophenyl ester the same number of parts of methane sulphonic acid 3 aminophenyl ester are used, the duration of the reaction is extended to 6 hours and otherwise the procedure is as described, then a very similar dyestuff is obtained which, to all intents and purposes, has identical fastness properties.

EXAMPLE 3 33 parts of 1,5 dinitro 4,8 dihydroxyanthraquinone and 27 parts of m-aminophenol are stirred for 8 hours at 130-135 in 500 parts of ethylene glycol monoethyl ether. The clear blue reaction mixture is concentrated by distilling off the greater part of the solvent in vacuo, the sirupy residue is stirred several times with 40 warm water which has been made weakly soda alkaline and then with 250 parts of methanol, and the pulverulent blue precipitate is filtrated off.

While still moist, the residue is slurried in 400 parts of 40 warm water and partly dissolved by the addition of 200 parts of pyridine. 37.4 parts of methane sulphonic acid chloride are added dropwise at 3540 while stirring well, the addition being made to the slurry within half an hour, the Whole is kept for another hour at this temperature and then the reaction mixture is diluted with 400 parts of ice water.

The dark blue reaction product which is precipitated in this way is filtered off and washed netural with water.

This product is again slurried in a mixture of 400 parts of water and 400 parts of pyridine at -95 and then 11.2 parts of sodium hydrogen sulphide are added all at once.

After 10 minutes, the mixture is diluted with 2000 parts OSOzCH;

ijsfitered oif, washed neutral with hot water and then The compound of the above formula obtained in a high yield in this way melts at 207-208. It dissolves in organic solvents with a clear blue, in concentrated sulphuric acid with a green colour.

Very pure blue dyeings are obtained from the aqueous dispersion of the dyestutf on polyglycol terephthalate fibres. The dyeings have particularly good sublimation and water fastness properties.

If the 27 parts of m-aminophenol are replaced by a mixture of 17 parts of m-aminophenol and 10 parts of p-aminophenol and otherwise the reaction is performed as described above, then a very similar dyestufl is obta1ned. Very strong dyeings are obtained from its aqueous dispersion on polyterephthalate and cellulose acetate fibres which have excellent sublimation, light and wet fastness properties.

EXAMPLE 4 If in Example 1, the 37.4 parts of methane sulphonic acid-B-aminophenyl ester are replaced by the same number of parts of methane sulphonic acid-4-aminophenyl ester and the condensation is performed at 60-65 with otherwise the same reaction partners, then a very similar dyestufi of the formula i riur-Q-osomm is obtained.

It melts at 179-180 and it dissolves in organic solvents with a reddish violet, in concentrated sulphuric acid with a dark blue colour.

From an aqueous dispersion, it dyes polyglycol terephthalate fibres in reddish violet shades which are very fast EXAMPLE 5 39.3 parts of methane sulphonic acid-4-aminophenyl ester are mixed with 33 parts of l,8-dinitro-4,5-dihydroxyanthraquinone and the mixture is poured all at once into 180 parts of nitrobenzene at 180. This temperature is maintained for 7 hours while stirring well, then the solvent is completely distilled ofi by introducing steam and the precipitated dyestutf of the formula is separated by filtration from the acidified solution. It is washed on the filter with very greatly diluted hydrochloric acid solution, then with greatly diluted hot sodium hydroxide solution and finally with hot water until the washing liquor is neutral.

Recrystallised from nitrobenzene, the dyestutf melts at 234236. It dissolves in organic solvents with a blue, in concentrated sulphuric acid with a greenish yellow colour.

From an aqueous dispersion, the dyestuff dyes polyglycol terephthalate fibres in blue shades which have excellent light, sublimation and wet fastness properties.

A very similar dyestutf is obtained if the dyestufi of the above formula is mixed in a ratio of 1:1 with the dyestuff mentioned in Example 3. Extraordinarily strong blue dyeings are attained with this dyestufi mixture on polyglycol terephthalate and cellulose acetate fibres which are very fast to sublimation, light and wet.

EXAMPLE 6 33 parts of 1,5-dinitiro-4,8-dihydroxyanthraquinone and a mixtureof 20.46 parts of methane sulphonic acid-3- aminophenyl ester and 28.93 parts of p-toluene sulphonic acid-4-aminophenyl ester are slurried in 160 parts of nitrobenzene, this mixture is heated to 190 within half an hour and kept at this temperature while stirring well for 5 hours. 160 parts of methanol are added at 70 to the clear dark blue solution obtained and then it is cooled to room 10 temperature whereupon the reaction product separates out as a fine blue powder. This is filtered off, washed with boiling methanol and water and then, while still moist, is slurried at -95 in 800 parts of a 50% aqueous pyridine solution.

A concentrated aqueous solution of 11.2 parts of sodium hydrogen sulphide is added dropwise to this suspension within 5 minutes while stirring strongly and then the reaction mixture is kept for another 5 minutes at 90-100". 1500 parts of ice water are then added to the greenish blue suspension, the precipitated mixture of the dyestuffs NH 0 OH (FSOQCI'L; H 0H 0 l mand NH; on

is filtered off at room temperature and washed with hot Water until the reaction is neutral.

Polyethylene glycol terephthalate and cellulose acetate fibres can be dyed from an aqueous dispersion of this mixture of dyestuffs in strong, clear blue shades which have extraordinary sublimation and wet fastness properties.

On alkylating these products with dimethyl sulphate, the corresponding N-monomethylamino-anthraquin0nes are obtained which have properties similar to the aminoanthraquinones described above.

EXAMPLE 7 16 parts of boric acid are added to a mixture of 18 parts of quinizarin, 6 parts of leucoquinizarin and 44.3 parts of chloromethane sulphonic acid-3-aminophenyl ester, and the mixture is stirred for 1 hour in 50 parts of ethyl alcohol at 80-85. At the end of this time, the reaction mixture shows a dark brown-violet colour. It is then mixed with parts of ethyl alcohol. After the addition of 0.5 part of sodium perborate, it is allowed to cool slowly at room temperature while being stirred.

The reaction product having the formula separates out in crystalline form and is filtered off, washed with boiling methyl alcohol, hot water which has been made weakly alkaline and, finally, with hot water until the washing liquor is neutral. Then the product is dried.

The dyestufi can in addition be recrystallized from ethylene glycol monoethyl ether, chlorobenzene or pyridine. It forms beautiful dark crystals having a greengolden shimmer. It dissolves in organic solvents with a clear reddish-violet, and in concentrated sulphuric acid with a dark blue colour.

From an aqueous dispersion, it dyes polyethylene glycol terephthalate fibres in clear violet shades which are very fast to sublimation, light and wet processing.

The same dyestuff is obtained, if 21.8 parts of 3-aminophenol are used instead of the 44.3 parts of chloromethane sulphonic acid-3-amonophenyl ester and the reaction is otherwise carried out as described. The product isolated by filtration is slurried in a mixture of 200 parts of water and pyridine (ratio 1:1) whereupon 22.35 parts of chloromethane sulphonic acid chloride are added dropwise within 1 hour at 5-10; the slurry is then heated for another two hours at 4050.

The reaction product which is separated out practically completely by dilution with 200 parts of water is obtained by filtration; it corresponds in every respect to the dyestufi's obtained by the first-described reaction.

EXAMPLE 8 33 parts of 1,5-dinitro-4,S-dihydroxyanthraquinone are slurried in 150 parts of nitrobenzene and, after the addition of 48.8 parts of chloromethane sulphonic acid-4- aminophenyl ester, this suspension is heated within half an hour to 180; the greater part of the reactants is thus dissolved. The reaction mixture is kept for 4 hours at this temperature while being stirred well, and the water formed during the reaction is continuously distilled off from the solution which gradually turns a clear blue colour.

On completion of the reaction, the solution is slowly cooled to room temperature with constant stirring, whereupon the reaction product of the formula Ht ran-@osm-cmm separates out in fine crystalline form. It is filtered off, washed with a mixture of nitrobenzene and methanol, then with methanol alone, then with 90 warm, strongly diluted aqueous sodium hydroxide solution and finally with hot water until the washing liquor is neutral.

The purity of the dyestufi so obtained can be further improved by recrystallisation. The fine blue-black crystals melt at 215216. The dyestuif dissolves in organic solvents with a clear blue, in concentrated sulphuric acid with a green colour.

From an aqueous dispersion, it dyes in particular polyethylene glycol terephthalate fibres in clear blue shades which have very good fastness to sublimation, light and wet processing.

It instead of the 48.8 parts of chloromethane sulphonic acid-4-aminophenyl ester, 58.5 parts of bromomethane sulphonic acid-3-aminophenyl ester are used, the duration of the reaction is extended to hours, and the procedure is otherwise as described, then a very similar dyestufl is obtained, which has practically identical fastness properties.

EXAMPLE 9 33 parts of 1,5-dinitro-4,8-dihydroxyanthraquinone and 27 parts of m-aminophenol are stirred for 8 hours at 130-135 in 500 parts of ethylene glycol monoethyl ether. The clear blue reaction mixture is concentrated by distilling off the greater part of the solvent in vacuo, while the sirupy residue is stirred several times with 40 warm water which has been made weakly soda alkaline, and then with 250 parts of methanol, whereupon the pulverulent blue precipitate is filtered ofi.

While still moist, the residue is slurried in 400 parts of 40 warm water and partly dissolved by the addition of 200 parts of pyridine. 44.3 parts of chloromethane sulphonic acid chloride are added dropwise within half an hour at 3540 while stirring well, and the mixture is kept for another hour at this temperature. Then it is diluted with 400 parts of ice water.

The dark blue reaction product which is precipitated in this way is filtered off and washed with water until it has become neutral.

This product is again slurried in a mixture of 400 parts of water and 400 parts of pyridine at -95 and then 11.2 parts of sodium hydrogen sulphide are added all at once.

After 10 minutes, the mixture is diluted with 2000 parts of ice water. A dyestufi precipitates which has the formula HgN y ?SO2CH2C1 m) I II-Ir-Q It is filtered off, washed neutral with hot water and dried. The compound of the above formula thus obtained in a high yield dissolves in organic solvent with a clear blue, in concentrated sulphuric acid with a green colour.

Very pure blue dyeings are obtained from the aqueous dispersion of the dyestuff on polyethylene glycol terephthalate fibres. The dyeings have particularly good sublimation and water fastness properties.

If the 27 parts of m-aminophenol are replaced by a mixture of 17 parts of m-aminophenol and 10 parts of p-aminophenol, and the reaction is otherwise performed as described above, then a very similar dyestufi is obtained. Very strong dyeings of excellent sublimation, light and wet fastness properties are obtained from its aqueous dispersion on polyethylene glycol terephthalate and cellulose acetate fibres.

EXAMPLE 10 2 parts of the finely milled mixture of dyestuffs obtained according to Example 6 are dispersed in 4000' parts of water. 12 parts of the sodium salt of o-phenylphenol and 12 parts of diammonium phosphate are added to this fine dispersion and 100 parts of a polyglycol terep'hthalate fabric are dyed for 1 /2 hours at -98". The dyeing is rinsed and thoroughly washed with dilute sodium hydroxide solution and a dispersing agent, eg the condensation product of naphthalene sulphonic acid and formaldehyde. A blue dyeing is obtained 'which is fast to light, wet and sublimation.

EXAMPLE 11 2 parts of the finely ground dyestuff obtained according to Example 1 are distributed in 4000 parts of water containing 2 parts of a condensation product of naphthalene sulphonic acid and formaldehyde. The pH of the dyebath is adjusted to 6.5 with acetic acid. parts of polyglycol terephthalate fabric are introduced at 40, the bath is heated in an autoclave to within 15 minutes and kept at this temperature for 45 minutes. The dyeing is rinsed with water and then soapcd. A clear 'violet dyeing is obtained which has excellent sublimation, light and wet fastness properties.

The following table shows the shades on polyethylene glycol terephthalate fibres which are obtained with other dyestuffs which can be produced by methods analogous to those described in the above examples.

TABLE-Continued (OSOzRh Shade 011 Example X1 X2 Y1 Y2 poly lycol No. -NH terep lthal- L ate fibres OSOzCHa 2e No, OH H H -NH Blue.

I OCH;

OSOQCH;

21 H H H H --NH- Violet.

( SOzCHg 050,011, 28 0H NHOHzCHzOH H H NH Blue.

29 H H H H NHOSO:CH;CH;CHCH; Violet.

OSOQCH: so 0H OH H H -NH- Blue-Violet.

OSOzCHra1 N01 OH H H NH Blue.

C(HI

a2 NH: OH H H Do.

33 H H H H -NH-CH; Violet.

a4 --No, OH H H --NH-OSO;CHI Blue.

35 H H H H -NH H1 Violet.

OSOzCHa 36 0H NH: H H -NH-- Blue.

1 Br 37 NHCHzCHaCHzOH OH H H -NH'OSO: D0.

CH 38 H H H H --NH- Violet.

39 H H H H Do SOzCHz 40 H H H --NH- D0.

I OSOzCH;

19 20 TABLE-Continued 050211). Shade on Example X; X; Y1 Y3 polyethylene No. -NH A yco L terephthelate fibres 55 NH, OH H H -NH D0.

OSOICIHICI as H OH H H -NH-osomrho1 Violet.

OISOzCHgBr a. OH NO, H H NH- Blue.

58 NHCII; OH H H NH--oso,oH,o1 Do 59 H H H H -NH--0S0,0H,Br Violet.

e0 H H c1 01 -NH--0so,omo1 Do.

(I311! 01 H H H H -NH-@-oso,omo1 Do.

62 NO: OH H H NHQ-OSO1OH;CI Blue.

According to a second aspect of the invention, valuable OH substituted oL-phenylamino-anthraquinone dyestufis are obtained by reacting an anthraquinone compound of the formula X 9 on I I I (SO:OR

X4 0 NH- A Y!-- 2 111m) and I H (I311 X X (1*) wherein X X X Y and Y have the same meanings as in I I I (SOr-O-R L.

Formula 1, H0 0 N with an amine of the formula 2 (1113*) (S O 20 R) n HzN wherein O OH in which formulas the respective symbols have the following meanings:

n, X and X have the same meanings as in Formulas III,

IIIA and IIIB, respectively;

R represents alkyl of from 4 to 10 carbon atoms, chlorolower alkyl, cycloalkyl of from 5 to 7 carbon atoms, phenyl, chlorophenyl, bromophenyl, fluorophenyl, lower alkylphenyl, lower alkoxyphenyl, chloro-lower alkylphenyl(lower alkyl-sulfonyD-phenyl, (lower alkyl-carbonyl)-phenyl, (lower alkanoyl-arnino)-phenyl, (lower alkyl sulfonyl) phenyl, (N lower alkyl sulfonyl-N- lower alkyl amino) phenyl, benzyl, chloro benzyl, bromo-benzyl, lower alkyl-benzyl, or pyridyl-(3)-, and

Z represents from one to two of the following substituents: hydrogen, lower alkyl, lower alkoxy, chlorine and bromine.

Where in the following specification, Formula 111* is referred to, Formulas IIIA and IIlB* are also meant.

Preferably, the benzene ring A is not further substituted or it contains methyl, methoxy, ethoxy or chlorine.

The greater part of the starting materials of Formula 1* usable according to the invention are known; examples OzN- with n mol of an organic hydroxyl compound ROH, R having the meaning given in Formula II, and subsequently reducing the nitro group to the amino group.

The reaction of starting materials of Formula 1* containing nitro groups with the amines of Formula II is performed, for example with an excess of amine in the melt at about 100-250 C., advantageously however, in an organic solvent which boils at about 110-220 C. Suitable organic solvents are, e.g. optionally halogenated or nitrated aromatic hydrocarbons such as xylenes, or monochlorobenzene or dichlorobenzenes, or nitrobenzene, also alcohols such as alkanols having at least 4 carbon atoms, e.g. butanol or amyl alcohol, or alkylene glycols and their monoalkyl ethers. The preferred organic solvent is nitrobenzene.

Starting materials of Formula 1* which do not contain nitro groups are reacted with the amines of Formula 11* preferably in the presence of boric acid or its alkali metal salts. In this reaction the starting materials of Formula 1* can also be used in the form of their leuco compounds or in admixture with their leuco compounds.

If amines of Formula 11* which are further substituted in both o-positions are used, the use of a 1,3-alkane diol with boric acid is recommended, which diol forms a cyclic ester, or of a 1,3-al-kane diol boric acid ester.

In the dyestuffs of Formula III*, if a nitro group symbolised by X or X is to be replaced by the amino group or by a low alkylamino, alkoxyalkylamino, or hydroxyamino group, this is done preferably by reducing the nitro group to the amino group and, if desired, substituting the latter by a low alkyl, alkoxyalkyl or hydroxyal-kyl group by means of an alkylating agent.

A modification of the process for the production of new substituted a-phenylamino-anthraquinone compounds containing no nitro group in the tar-position consists in reacting an anthraquinone compound of formula of X and X one is hydrogen or the hydroxyl group, the other is hydrogen, the hydroxyl group andif the first X is the hydroxyl group-also the amino group which is unsubstituted or one which is substituted by a low alkyl, alkoxyalkyl or hydroxyalkyl group,

Y and Y are hydrogen or, if each of X and X are hydrogen, they also represent halogen, and

wherein Hal is chlorine or bromine and n1 is 1 or 2 and the benzene ring {X is unsubstituted or is further substituted by halogen or by low alkyl or low alkoxy groups, with an organic hydroxyl compound of formula wherein R is an aliphatic radical containing at least 4 carbon atoms, an araliphatic, a cycloaliphatic or a car- 22 bocyclic-aromatic radical, or reacting such anthraquinone compound of Formula IV* with an alkali metal salt of this organic hydroxyl compound of Formula V* to form a compound of Formula 111' solo-R) wherein X X Y Y R, n and A have the meanings given in Formulae IV and V and, optionally, introducing a low alkyl, alkoxyalkyl or hydroxyalkyl group as substituent into the unsubstituted amino group symbolised by X or X in Formula III.

The starting compounds of Formula IV* are obtained, for example, by reacting an anthraquinone compound of Formula I with an amine of the formula Naturally, the reaction conditions described in the first process pertain here too. On using an anthraquinone compound of Formula 1* wherein one of X and X is the nitro group, the latter is then reduced to the amino group and, optionally, this is substituted by a low alkyl, alkoxyalkyl or hydroxyalkyl group, and the ot-phenylamino-anthraquinone compounds are then converted in the known way, e.g. by reaction with chlorosulphonic acid or bromosulphonic acid into their sulphonic acid chlorides or bromides.

The condensation of the sulphonic acid chloride or bromide of Formula IV* with the compound of Formula V or with an alkali metal salt of this compound is performed in the usual way, e.g. in an organic solvent which is inert to both reaction partners, optionally in the presence of an acid binding agent, preferably in aqueouspyridine or aqueous-alkaline solution or suspension.

The new a-phenylamino-anthraquinones of Formula III generally crystallise out of the reaction mixture. They are isolated by filtration, dilution of the mixture with water or with a low alcohol or by removal of the organic solvent by distillation or steam distillation, and they can be purified by recrystallisation.

In a purse state, the new dyestuffs are shimmering, crystalline, deeply coloured compounds. They dissolve in hot organic solvents with a pure violet to blue colour. From an aqueous dispersion they dye polymeric ester fibres, for example cellulose ester fibres such as cellulose triacetate, preferably however, fibres from polymeric esters of aromatic polycarboxylic acids with polyvalent alcohols, e.g. polyethylene glycol terephthalate fibres, in violet to blue shades.

Fibres from polymeric esters of aromatic polycarboxylic acids with polyvalent alcohols are dyed with the aqueous dispersions of the dyestuffs according to the invention preferably at temperatures of over C. under pressure. Very good dyeings are also obtained if these fibres are impregnated with concentrated aqueous dispersions of the dyestuffs according to the invention, the fabric is squeezed out, dried and then the dyeing is fixed at temperatures of 2SO C. The dyeing can also be performed, however, at the boiling point of the water in the presence of carriers such as phenylphenol, polychlorobenzene compounds or similar auxiliaries.

In many cases the drawing power of the dyestuffs as well as their dispersibility in the dye liquor can even be improved by mixing two or more dyestuffs of which at least one corresponds to Formula 111*. Compared with dyeings made with previously known dyestuffs of similar constitution, the violet to blue dyeings attained on the fibres mentioned with the dyestuffs according to the inven- 23 tion have considerably improved fastness to sub-limitation and light and have very good wet fastness properties.

In addition, compared with previously known dyestuffs, wool is considerably better preserved with the dyestuffs according to the invention.

The following examples illustrate the invention. Where not expressly stated, parts are given as parts by weight. The temperatures are in degrees centigrade. The relationship of parts by weight to parts by volume is as that of grammes to cubic centrimetres.

EXAMPLE 1 65.8 parts of 3-aminobenzene sulphonic acid-p-methylphenyl ester are thoroughly mixed with 33 parts of 1,5- dinitro-4,8-dihydroxy-anthraquinone in 300 parts of nitrobenzene and the mixture is stirred at 100 and slowly heated to 180-190. The mixture is kept at this temperature for 12 hours, then the main amount of solvent is distilled off in vacuo, the dark blue residue is then stirred with 150 parts of ethylene glycol monoethyl ether at the boil and the reaction mixture is then cooled to room temperature.

The finely crystalline dyestuff which precipitates, of the formula OH O NH- SO20-QCH3 is filtered off, washed with ethylene glycol monoethyl ether, methanol and finally with water, and dried. It

melts at 2054206 and dissolves in organic solvents with which is precipitated in this way in a fine form, is filtered off and washed neutral with hot water.

It is a dark blue powder which can be crystallised from nitrobenzene whereupon it then melts at 204-205 and dissolves in organic solvents with a clear blue, in concentrated sulphuric acid with a blue-green colour.

From an aqueous dispersion it dyes polyglycol terephthalate fibres in particular in clear blue shades which have very good sublimation, light and wet fasteness properties.

On mixing this dyestuff with l-(m-methylsulphonyloxy)-phenylamino-4,S-dihydroxy-S aminoanthraquinone, which is a dyestuff of related structure, a dyestufr is obtained which dyes polyglycol terephthalate fibres and cellulose acetate fibres in very strong blue shades having excellent fastness properties.

EXAMPLE 2 50 parts of 3-aminobenzene sulphonic acid phenyl ester and 33 parts of 1,5-dihydroxy-4,S-dinitroanthraquinone in 450 parts of nitrobenzene are heated for 8 hours at 190-200. The mixture is then cooled to 90l00 and 300 parts of methanol are added all at once. The reaction mixture is then very slowly cooled to room temperature again within 23 hours whereupon the reaction product precipitates in the form of beautiful crystals which are filtered off and washed with methanol until the washing water is colourless.

The reaction product, while still moist, is then stirred into a mixture of 400 parts of water and 400 parts of pyridine, the slurry is warmed to 90 and at this temperature, 3.4 parts of sodium hydrogen sulphide are added to the mixture while stirring vigorously. After a further 5 minutes at this temperature, 800 parts of ice water are added to the mixture and the mixture of dyestuffs of the formula s rozo on so 0- n G OH 0 Nil-Q and which is precipitated is filtered off. It is a dark blue powder and polyglycol terephthalate fibres are dyed from an aqueous dispersion thereof in strong, clear blue shades which have excellent sublimation, light and wet fastness properties.

EXAMPLE 3 40 parts of 3-aminobenzene sulphonic acid-p-methylphenyl ester, 16 parts of quinizarin and 8 parts of leuco quinizarin are heated to 50 in 70 parts of ethanol and 16 parts of boric acid are added all at once. The temperature is slowly raised to 85 while stirring slowly and this temperature is maintained for 5 hours. After the addition of 500 parts of ethanol, the reaction mixture is cooled to room temperature within 3 hours, whereupon the dyestuif of the formula precipitates in crystalline form. It is filtered off, washed with ethanol and dried. After recrystallisation from ethylene glycol monoethyl ether it melts at 168l69. It dissolves in organic solvents with a clear red-violet, in concentrated sulphuric acid with a violet-blue colour. It dyes polyglycol terephthalate fibres from an aqueous dispersion in clear, reddish violet shades which are very light, sublimation and wet fast.

A dyestuff which has the same good fastness properties and, at the same time, increased drawing power onto polyglycol terephthalate fibres is obtained by mixing equal parts of the dyestuff and the isomeric compound formed by monocondensation of quinizarin and p-toluene sulphonic acid-3-aminopheny1 ester.

EXAMPLE 4 18 parts of quinizarin, 6 parts of leuco quinizarin, 58.6 parts of 2-amino-5-methylbenzene sulphonic acid 25 guaiacol ester and 16 parts of boric acid are stirred in 80 parts of ethanol for 8 hours at 80-85". After adding 200 parts of ethanol and a few drops of piperidine, air is directed for 1 hour at 40-50 through the mixture whereupon the latter 'is cooled to room temperature.

26 It is slurried in 500 parts of an aqueous 50% pyridine solution and 11.2 parts of sodium hydrogen sulphide are added and the whole is kept for 10 minutes at a temperature of 90100.

On diluting with 1500 parts of cold water, the dyestuff 5 The dyestulf of the formula of the formula l H I smo-o1 d 1 111 -orr3 OH O 01136 I precipitates in crystalline form. It is filtered off, washed with water until the washing water has a neutral reaction and dried. GEM) It dissolves in organic solvents with a clear blue, in concentrated sulphuric acid with a blue green colour. It precipitates in the form of brownish v1olet crystals. It 1s dyes polyglycol terephthalate fibres from an aqueous di separated from the mother liquor by filtration. The prepersion in clear blue shades which have excellent light, cipitate is washed with ethanol, very greatly diluted sosublimation and wet fastness properties. dium hydroxide solution and then with water until the On alkylating this product with dimethyl sulphate, the washing water has a neutral reaction whereupon it is corresponding N-monomethylaminoanthraquinone comdried. pound is obtained which has properties similar to those It dissolves in organic solvents with a violet, in concenof the aminoanthraquinone compound described above. trated sulphuric acid with a blue colour. It dyes polyglycol EXAMPLE 6 terephthalate fibres from an aqueous dispersion in pure violet shades which have good sublimation, light and wet 2 P Of the finely mined dyestufi mlxtlll'e Obtalned fastness properties. according to Example 2 are dispersed in 4000 parts of The same dyestuif is also obtained in the following way: Wa 12 parts of the sodium salt of o-phenylphenol and 32.9 parts of 1-hydroxy-4-p-toluidino-anthraquinone are 12 parts of diammonium phosphate are added to thls fine added at 10l5 to 100 parts of chlorosulphonic acid and 5 dispersion and 100 Parts of polyglycol tere'phqlalate f the Whole is kept for 4 hours at this temperature. The 3 aer dyed for 1 /2 hours at 95 98". The dyeing is rinsed dark blue solution is poured onto ice, the precipitate and thoroughly washed with dllute sodium hydroxide soformed is filtered 01f, washed neutral and dried in vacuo. 111 011 and a dispersing agent, eg. the condensation prod- This product is added in small portions to a solution of uct of naphthalene sulphonic ac d and formaldehyde. A 16 parts of the sodium salt of guaiacol in 100 parts of 40 blue dyeing which is fast to sublimation, light and wet is a 50% aqueous pyridine at 0-10 and then the solution tain d. is heated to 4050 for 30 minutes. On diluting the reac- EXAMPLE 7 mlxtur? 500 P i of f the dyestufi 18 2 parts of the finely milled dyestutf obtained according most quantitat vely precipitated. It is filtered off, Washed to Example 3 are dispersed in 4000 Parts of Water which neutral and contains 2 parts of a condensation product of naphtham all Its propetrles to the Product lene sulphonic acids and formaldehyde. The pH of the tamed by the first methoddyebath is adjusted to 6.5 with acetic acid. 100 parts of EXAMPLE 5 polyglycol terephthalate fabric are introduced at 40, the

bath is heated 1n an autoclave to 120 within 15 min- 785 parts of 3-amino-4-methoxybenzene sulphonic utes and kept for 45 minutes at this temperature. The acid-p-chlorophenyl ester are added to a slurry of 33 parts dyeing is rinsed with water and then soaped. In this way of 1,5-dihydroxy-4,8-dinitro-anthraquinone in 400 parts of a clear violet dyeing is obtained which has excellent light, ethylene glycol monoethyl ether and the reaction mixture wet and sublimation fastness properties. is stirred for 24 hours at the boiling temperature of the The following table shows the shades on polyglycol solvent. On cooling the solution, the condensation prodterephthalate fibres obtained with other dyestuffs which uct precipitates in a finely crystalline form and is isolated are produced analogously to the method described in the by filtration. above examples.

TABLE X 0 OH I ll I I Y I (SOZOR)1| X2 0 NH- SOzOR)n Shade on Example X X2 Y1 Y2 polyglycol No. NH terephthalate fibres 8 H H H Cl --NH Violet.

33 34 TABLEContinued SO 11)., Shade on Example X1 X2 Y1 Y2 polyglycol No. NH terephthalate fibres SO OCHr-QCI-I 47 H H 01 01 NH- Violet.

smoom-Qm 48 NH; OH H H -NH Blue.

EXAMPLE 49 20 NH: 0 on A mixture of 33 parts of 1,5-dinitro-4,8-dihydroxyanth-raquinone and 48.9 parts of 3-amino-6-methylbenzene sulphonic acid phenyl ester in 90 parts of nitrobenzene is 080mm stirred for 30 hours at 170-175 then the nitrobenzene is distilled off by the introduction of steam. The resulting 9 suspension of the condensation product in about 1000 parts of water is stirred with equal parts of pyridine, the dyestuif partly dissolves with a blue colour, and is then mixed at once with 11.2 parts of sodium hydrogen sulphide at a temperature of 85 to 90. The reduction is completed after a few minutes at this temperature. Upon cooling of the solution and dilution with 1000 parts of cold water, the dyestuff having the formula NH2 0 OH separates almost quantitatively and is filtered oif and dried.

It melts at 210-211" and dissolves in organic solvents with a reddish blue colour, in concentrated sulphuric acid with a blue-green colour.

If it is dispersed in water, it dyes polyethyleneglycol terephthalate'fibres in blue shades which have good light, sublimation and wet fastness properties.

EXAMPLE 50 39.45 parts of 3-amino-6-methylbenzene sulphonic acid phenol ester, 18.7 parts of methane sulphonic acid-B-aminophenol ester and 33 parts of 1,5-dinitro-4,8-dihydroxyanthraquinone in 100 parts of nitrobenzene are stirred for 20 hours at 170-175 Then the reaction mixture is diluted with 175 parts of methanol, and the reaction products separate as a solid from the solution. They are isolated by filtration and again slurried at 90-95 in 100 parts of a 50% aqueous solution of pyridine. 11.2 parts of sodium hydrogen sulphide are added at once to this suspension, which is subsequently stirred for 15 minutes at 9095. By dropwise addition of 50 parts of water and cooling to room temperature, the reduction products are separated almost completely and are isolated by filtration. The mixture of dyestuffs obtained corresponds to the formulae NH: 0 OH I II I l l I I OH 0 run-4311;

This mixture dissolves in organic solvents with a clear blue colour, in concentrated sulphuric acid with a bluegreen colour.

If this dyestutf mixture is dispersed in water, it dyes cellulose triacetate fibres and polyethyleneglycol terephthalate fibres in deep blue shades which have good light, sublimation and wet fastness properties.

EXAMPLE 5 1 1phenylamino-4-hydroxyanthraquinone is converted in the known way with chlorosulfonic acid into the corresponding dyestuif sulfonic acid chloride. 19 parts of 3- hydroxypyridine are added to the slurry of 36.4 parts of the finely pulverized sulfonic acid chloride so obtained in a solution of 200 parts of water, parts of ethanol and 19 parts of sodium hydroxide. The reaction mixture is heated to 70-80 while stirring strongly, and stirring is continued for 12 hours at this temperature. After cooling the reaction mass, the dyestuff is filtered off under suction, washed with a lot of water and dried in vacuo. Its composition corresponds to the formula The dyestuff is abrown-violet powder. In finely distributed form it dyes polyglycol terephthalate fibers such as Terylene in clear violet shades. The dyeings are distinguished by particularly good fastness to light and sublimation.

If in the above process, the sulfonic acid chlorides obtained from 1-(2'-methyl-6'-phenylamino)4-hydroxyanthraquinone, 1 (2 ',6'-dimethylphenylamino)-4-hydroxyanthraquinone or 1 (2',4',6-trimethylphenylamino)4- hydroxyanthraquinone are used, then products are obtained which have similar dyeing properties. Starting from the acid chlorides obtained by treatment of l-phenylamino-4,8dihydroxy-S-aminoanthraquinone or l-phenylamino-4-aminoanthraquinone with chlorosulfonic acid, under the above conditions blue dyestuffs having similar dyeing properties are obtained.

EXAMPLE 52 35 parts of the sulfonic acid chloride obtained by treating l-amino-2-phenoxy-4-hydroxyanthraquinone with chlorosulfonic acid, 19 parts of 3-hydroxypyridine and 19 parts of sodium carbonate in 150 parts of ethanol and 200 parts of water are heated for 10 hours at 80. The red dyestuff which precipitates after cooling the reaction mixture is filtered off, washed first with ethanol and then with a lot of water and dried in vacuo at 70. The product obtained corresponds to the formula it H III 0 OH I (OSOz-Rh H 0 (b) a dyestulf of the formula X o OH I (osoa-lv)n X4 NH A g and (c) a dyestutf of the formula I (OSO2-R )u OH 0 as wherein one of X and X is hydroxy and the other is a member selected from the group consisting of hydroxy, nitro, amino, lower alkyl-substituted amino, lower alkoxylower alkyl-substituted amino, and hydroxy-lower alkylsubstituted amino,

each of Y and Y is a member selected from the group consisting of hydrogen, chloride and bromine,

R is a member selected from the group consisting of lower alkyl, lower alkenyl, chloro-lower alkyl, chloro-lower alkenyl, cycloalkyl of from 5 to 7 carbon atoms, phenyl, chlorophenyl, bromophenyl, fiuorophenyl, lower alkyl phenyl, lower alkoxyphenyl, chloro-lower alkylphenyl,

lower alkylsulfonyl-phenyl, lower alkylcarbonyl-phenyl, lower alkanoylamino-phenyl, and N-lower alkylsulfonyl-N-lower. alkylphenyl,

Z represents from one to two substituents selected from the group consisting of hydrogen, lower alkyl, lower alkoxy, chlorine, bromine and lower alkylsulfonyl, and

n is one of the integers 1 and 2.

2. A dyestutf of the formula 3. A dyestuff of the formula 0 NHOSO2CI-Ia 4. A dyestufi of the formula 0 H m OSOaCH: 6H

5. A dyestutf of the formula NH; (l) OH 6. A dyestuff of the formula o NH-Q-OSOzCHa 7. A dyestutf of the formula NH: O

OH I I 8. A dyestuff of the formula 9. A dyestulf composition consisting essentially of a dyestuff of the formula NH: (I311 OSzCHa mixed with a dyestuff of the formula NH: I

in a weight ratio of about 1:1.

10. A dyestutf having affinity for polyester fibers, and being a memiber selected from the group consisting of (a) a dyest-uif of the formula ya I (SO2O-R2) u wherein one of X and X is hydroxy and the other is a member selected from the group consisting of hydroxy, nitro, amino, lower alkyl-substituted amino, lower alkoxylower alkyl-sulbstituted amino, and hydroxy-lower alkylsubstituted amino,

each of Y and Y is a member selected from the group consisting of hydrogen, chlorine and bromine,

R is a member selected from the group consisting of alkyl of from 4 to 1-0 carbon atoms, chloro-lower alkyl,

cycloalkyl of from 5 to 7 carbon atoms, phenyl, chlorophenyl, bromophenyl, fluorophenyl, lower alkylphenyl, lower al'koxyphenyl, chloro-lower alkyl-phenyl, lower alkyls'ulfonyl-phenyl, lower alkylcarbonyl-phenyl, lower alkanoylamino-phenyl, lower alkylsulfonyl-amino, N- lower alkylsulfonyl-N-lower alkyl-amino-phenyl, benzyl, chloro-benzyl, bromo-benzyl, lower alkyl-benzyl and pyridyl-3,

Z represents from one to two suIbstit-uents selected from the group consisting of hydrogen, lower alkyl, lower alkoxy, chlorine and bromine, and

n is one of the integers 1 to 2.

38 11. A dyestufi of the formula somQcm G 12. A dyestuff of the formula am I tH 13. A dyestuif of the formula amt NH 3 14. A dyestuff of the formula NR2 0 (|)H smoQ-om 15. A dyestulf of the formula NH: (H) OH (5H IIHQCHS 16. A dyestuff of the formula OH 0 o -Q Nat IIHQm,

17. A- dyestuff composition consisting essentially of a dyestuff of the formula in a weight ratio of about 1:1.

(References on following page) 39 References Cited UNITED STATES PATENTS 3/ 1940 Weinand 260-371 1/1956 Hoefie et a1. 260-373 9/ 1963 Lodge 260-374 8/ 1966 Hindermann et a1. 8-39 10/1966 Hindermann et a1. 260-380 FOREIGN PATENTS 6/ 1963 Great Britain. 10/ 1962 France.

40 1,309,676 10/1962 France.

394.441 (n.a.) Switzerland.

5 LORRAINE A. WEINBERGER, Primary Examiner.

H. C. WEGNER, Assistant Examiner.

US. Cl. X.R. 

